Methods of using reactive surfactants in subterranean operations

ABSTRACT

Novel uses of reactive surfactants in treating subterranean formations and/or proppant particulates are provided. In one embodiment, the present invention provides a surfactant-treated proppant particulate comprising a proppant particulate that comprises at least one surface that has been allowed to interact with a reactive surfactant.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 11/133,554, entitled “Methods of Modifying Fracture Faces andOther Surfaces in Subterranean Formations,” filed on May 20, 2005 byWeaver et al., and U.S. patent application Ser. No. 11/133,697, entitled“Methods of Treating Particulates and Use in Subterranean Formations,”filed on May 20, 2005, by Weaver et al., the entireties of which areherein incorporated by reference for all purposes. The present inventionis related to co-pending U.S. application Ser. No. ______, AttorneyDocket No. HES 2005-IP-017362U1P1 entitled “Methods of Using ReactiveSurfactants in Subterranean Operations,” filed concurrently herewith,the entire disclosure of which is incorporated herein by reference.

BACKGROUND

The present invention relates to methods and compositions useful insubterranean operations, and more particularly, to novel uses ofreactive surfactants in treating subterranean formations and/or proppantparticulates.

Hydrocarbon wells are often located in subterranean formations thatcontain unconsolidated particulates (e.g., sand, gravel, proppant,fines, etc.) that may migrate out of the subterranean formation into awell bore and/or may be produced with the oil, gas, water, and/or otherfluids produced by the well. The term “unconsolidated particulates,” andderivatives thereof, is defined herein to include loose particulates andparticulates bonded with insufficient bond strength to withstand theforces created by the flow of fluids through the formation.Unconsolidated particulates may comprise, among other things, sand,gravel, fines, and/or proppant particulates in the subterraneanformation, for example, proppant particulates placed in the subterraneanformation in the course of a fracturing operation, among other purposes,to hold open conductive fractures created in that operation (e.g.,forming a “proppant pack” within the fracture).

The presence of unconsolidated particulates in produced fluids may beundesirable in that, among other problems, the particulates may abradepumping and other producing equipment and/or reduce the production ofdesired fluids from the well. Moreover, particulates that have migratedinto a well bore, among other things, may clog portions of the well boreand/or a proppant pack, reducing the conductivity of the subterraneanformation (i.e., the ability of fluids to flow through the formation).

Several different treatments are used in the art to control themigration of unconsolidated particulates in subterranean formations. Onesuch method involves placing a filtration bed containing gravel (e.g., a“gravel pack”) near the well bore to present a physical barrier to thetransport of unconsolidated particulates with the production of desiredfluids. Typically, such “gravel-packing operations” involve the pumpingand placement of a quantity of certain particulate, into theunconsolidated subterranean formation in an area adjacent to a wellbore. One common type of gravel-packing operation involves placing ascreen in the well bore and packing the surrounding annulus between thescreen and the well bore with gravel of a specific size designed toprevent the passage of formation sand. The screen is generally a filterassembly used to retain the gravel placed during the gravel-packoperation. A wide range of sizes and screen configurations are availableto suit the characteristics of the gravel-pack sand used. To install thegravel pack, the gravel is carried to the formation in the form of aslurry by mixing the gravel with a viscous treatment fluid. Once thegravel is placed in the well bore, the viscosity of the treatment fluidis reduced, and it is returned to the surface. The resulting structurepresents a barrier to migrating sand from the formation while stillpermitting fluid flow. However, the use of gravel packs and/or screensmay exhibit problems such as screen plugging and screen erosion, or maybe time-consuming and expensive to install.

Other methods used to control unconsolidated particulates insubterranean formations involve consolidating unconsolidatedparticulates into stable, permeable masses by applying a resin or atackifying agent to the subterranean formation, which may causeunconsolidated particulates to adhere to one another, inter ali,presenting their migration into produced fluids. However, the use ofconventional resins and tackifying agents may be problematic. Forexample, these treatments may require applying several differentcomponents (e.g., preflush fluids, afterflush fluids, catalysts, and thelike) to the subterranean formation, which may add cost and complexityto the operation and/or require longer periods of time. Also,conventional multi-component treatments may not be practical due to thedifficulty in determining if the entire interval has been treated withall of the components used.

Surfactants have been used heretofore in the art for many purposes,including stabilizing foams or emulsions, changing the wettability ofsurfaces, solubilizing certain materials, dewatering fluids, reducingthe surface tension of fluids, increasing the viscosity of fluids,enhancing viscoelastic and rheological properties of fluids, and/oraiding in the placement of treatment fluids in subterranean formations.However, in some instances, conventional surfactants may destabilize acoating (e.g., resin or tackifying agent) on a surface within asubterranean formation or a surface of a proppant particulate, forexample, by forming surfactant micelles within the coating and/or makingthe coating less dense. In other instances, it may be desirable todeposit molecules of a surfactant on a surface within a subterraneanformation and/or a surface of a proppant particulate, for example, whenthe proppant particulate is to be treated with certain aqueoustackifying agents. However, molecules of conventional surfactants maynot distribute themselves evenly along the coating, which may leavecertain portions of a subterranean formation or a proppant particulateinsufficiently treated with the surfactant for particular subterraneanoperations.

SUMMARY

The present invention relates to methods and compositions useful insubterranean operations, and more particularly, to novel uses ofreactive surfactants in treating subterranean formations and/or proppantparticulates.

In one embodiment, the present invention provides a proppant particulatecomprising at least one treated surface that has interacted with areactive surfactant.

In another embodiment, the present invention provides a treatment fluidcomprising a base fluid and a reactive surfactant.

In another embodiment, the present invention provides a treatment fluidcomprising a base fluid and a proppant particulate that comprises atleast one treated surface that has interacted with a reactivesurfactant.

The features and advantages of the present invention will be apparent tothose skilled in the art. While numerous changes may be made by thoseskilled in the art, such changes are within the spirit of the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to methods and compositions useful insubterranean operations, and more particularly, to novel uses ofreactive surfactants in treating subterranean formations and/or proppantparticulates.

The methods, treatment fluids, and surfactant-treated proppantparticulates of the present invention generally involve the use of areactive surfactant. The term “reactive surfactant” is defined herein toinclude any surfactant whose molecules are capable of forming polymers,copolymers or crosslinks with itself or with other molecules. In certainembodiments of the present invention, the reactive surfactant is allowedto interact with a surface in a subterranean formation (e.g., a fractureface), a wellbore wall, or a particulate (e.g., sand, gravel, fines,proppant particulates, etc.) being treated. The term “interact with asurface,” as used herein, does not imply any particular action, and isdefined herein to include any number of different chemical and/ormechanical interactions between the reactive surfactant and the surfacebeing treated. For example, the reactive surfactant may form a “coating”on the surface being treated, which is defined herein to include anyfilm or layer that covers some portion of the surface. In certainembodiments, the reactive surfactant may become absorbed into thesurface being treated (or some other coating thereon). In certainembodiments, at least some portion of the reactive surfactant may resideon a surface of a proppant particulate that has been allowed to interactwith a reactive surfactant. The results of this interaction may, interalia, help “consolidate” unconsolidated particulates, as that term isdefined herein, (e.g., by forming a tacky or curable coating that causesunconsolidated particulates to adhere to each other), modify thehydrophobicity or hydrophilicity of the surface, provide a site forsubsequent reaction with one or more compounds, and/or maintain theconductivity of a subterranean formation, gravel pack, and/or proppantpack. Among other things, this coating may exhibit greater colloidalstability and/or comprise more densely packed polymer molecules thancoatings generated using conventional materials. Moreover, the moleculesof the reactive surfactants used in the present invention may distributethemselves more evenly along the surfaces treated herein than moleculesof a conventional surfactant, which may create a more uniform and/ormore stable coating.

The reactive surfactants suitable for use in the present inventioncomprise any surfactant whose molecules are capable of forming polymers,copolymers, or crosslinks with itself or with other molecules. Examplesof reactive surfactants that may be suitable for use in the presentinvention include, but are not limited to the following: diallyl aminepluronics; linoieic alcohols; allyl alkyl phenols; acrylate derivatives;allyl alcohol alkenyl anhydride derivatives; maleic derivatives;sulfosuccinate derivatives; allyl amine salts; polymerizable esters(e.g., olefinically unsaturated esters, alkenylsuccinic monoesters);ethylenically unsaturated amine salts of sulfonic, phosphoric andcarboxylic acids; alpha-beta ethylenically unsaturated poly(alkylenoxy)compounds; ring sulfonated maleate half esters of alkoxylated alkylarylols; ring sulfonated half esters of maleic anhydride withalkoxylated alkyl arylols; aliphatic diols; polyoxyalkylene alkylethers; and mixtures thereof. The term “derivative” is defined herein toinclude any compound that is made from one of the listed compounds, forexample, by replacing one atom in the listed compound with another atomor group of atoms, rearranging two or more atoms in the listed compound,ionizing the listed compounds, or creating a salt of the listedcompound.

Certain reactive surfactants that may be suitable for use in the presentinvention may comprise at least one branched aliphatic hydrocarbon groupor branched aliphatic acyl group. Certain reactive surfactants that maybe suitable for use in the present invention may comprise unsaturatedcompounds having a pentenyl group to which an alkylene oxide is added.Certain reactive surfactants that may be suitable for use in the presentinvention may comprise polyhydroxyl functional non-ionic surfactantshaving repeating polymer units in the backbone and from 3 to 31 hydroxylgroups wherein the hydroxyl groups on the repeating polymer unit areseparated by 4 or more carbon atoms wherein the reactive surfactant issubstantially free of oxyethylene units. Certain reactive surfactantsthat may be suitable for use in the present invention may comprisesubstantially linear synthetic water-soluble surfactants whose polymericbackbones are derived from the polymerization of one or moreethylenically unsaturated monomers and have an average molecular weightof from about 500 to about 40,000. Certain reactive surfactants that maybe suitable for use in the present invention may comprise polymerizablesurfactants formed by the reaction of a diallylamine, ethylene oxide,propylene oxide, and/or butylene oxide. Certain reactive surfactantsthat may be suitable for use in the present invention may compriseethylenically unsaturated polymerizable water-soluble nonionicsurfactants formed by the reaction of a diallylamine compound withethylene oxide, propylene oxide, or butylene oxide in an emulsionpolymerization reaction. Certain reactive surfactants that may besuitable for use in the present invention may comprise one or morepolymerizable antimicrobial quaternary ammonium compounds derived fromat least one acid, wherein the acid is a sulfonic acid, a carboxylicacid, a phosphoric acid, or a salt therof, wherein the acid (or saltthereof) comprises at least one ethylenically unsaturated portion.Another type of reactive surfactant that may be suitable for use in thepresent invention are amine salts comprising: (a) at least one acid thatis a sulfonic acid, a carboxylic acid, or a phosphoric acid, or amixture thereof; and (b) at least one nitrogenous base that comprises atleast one nitrogen atom and at least one ethylenically unsaturatedportion. Another type of reactive surfactant that may be suitable foruse in the present invention are esters of acrylic, methacrylic, andcrotonic acids and the mono- and di-esters of maleic, fumaric, itaconic,and aconitic acids with one or more of the following: (a) C₈-C₂₀alkylphenoxy (ethyleneoxy)10-60 ethyl alcohol; (b) (ethyleneoxy)₁₅₋₂₅sorbitan esters of C₁₂-C₂₀ fatty acids; or (c) methyl cellulose,hydroxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol.

One type of reactive surfactant that may be suitable for use in thepresent invention are reactive surfactants that comprise: (a) oneanionic hydrophilic group; and (b) one reactive group selected from thegroup of a vinyl group, an allyl group, and groups having formula (1)below:

wherein R¹ and R² are each a hydrogen atom or CH₂X (wherein X is ahydrogen atom or a substituent), Y is a carbonyl group or methylenegroup, and p is a number equal to zero or 1.

Another type of reactive surfactant that may be suitable for use in thepresent invention are phosphoric esters having formula (2) below:

wherein: R is a hydrogen atom or a methyl group; AO is a C₆-C₁₈oxyalkylene group or oxy(alkoxymethyl)ethylene group; AO′ is a C₂-C₄oxyalkylene group; M is a hydrogen atom, an alkali metal atom, orammonium; m is a number equal to 0 or from 1 to 3; and n is a numberfrom 1 to 100.

Another type of reactive surfactant that may be suitable for use in thepresent invention are sulfate surfactants having formula (3) below:

wherein: R₁ is a C₆-C₂₂ alkyl group; R₂ is a hydrogen atom or a methylgroup; A is an ethylene group and/or a propylene group; a is an integerfrom 1 to 20; b is 0 or an integer from 1 to 20; and M is a hydrogenatom, an alkali metal atom, an alkaline earth metal atom, ammonium, aresidual group of an alkyl amine, or a residual group of analkanolamine.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (4) or (5) below:

wherein: A₁ is a C₅-C₁₈ alkylene group or an alkoxymethylethylene group(whose alkoxy group has 4-18 carbon atoms); A₂ is a C₂-C₄ alkylenegroup; n is a number from 0 to 200; and M is a cation.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (6) below:

wherein: n and m are each any number; X denotes a methylene group orcarbonyl group; AO is an oxyalkylene group or oxy(alkoxymethyl)ethylenegroup; and R₁-R₆ are each alkyl groups. Reactive surfactants of thistype comprise at least one substituted or unsubstituted aryl cyclicsulfonium zwitterion groups in the molecules of the reactive surfactant.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (7) below:

wherein: a, b, and m are each any number; AO is an oxyalkylene group oroxy(alkoxymethyl)ethylene group; and M is a hydrogen atom, an alkalimetal atom, an alkaline earth metal atom, ammonium, a residual group ofan alkyl amine, or a residual group of an alkanolamine. Reactivesurfactants of this type comprise both a long-chain alkyl group and apolymerizable reactive group having a hydrophilic polyoxyalkylene chain.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (8) and/or (9) below:

wherein: R¹ is a branched aliphatic hydrocarbyl group or a secondaryaliphatic hydrocarbyl group; R² is an alkylene group; R³ is ahydrogenator or a methyl group; AO and AO′ are each a C₂-C₄ oxyalkylenegroup; M is a hydrogen atom, an alkali metal, an alkaline earth metal,or an ammonium; m and n are each a number from 0 to 100; and a and b areeach a number equal to 0 or 1.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants prepared by formulating a phosphoricester-type reactive surfactant having formula (10) below with a sulfuricester-type surfactant having formula (11) below in a prescribed ratio:

wherein: A¹ is a C₅-C₁₈ alkylene group or an alkoxymethylethylene group(whose alkoxy group has 4-18 carbon atoms); A² is a C₂-C₄ alkylenegroup; X denotes a methylene group or a carbonyl group; M¹ and M² areeach a hydrogen atom, an alkali metal atom, an alkaline earth metalatom, ammonium, a residual group of an alkyl amine, or a residual groupof an alkanolamine; and e, f, g, m, and n are each any number. Anothertype of reactive surfactant that may be suitable for use in the presentinvention are unsaturated compounds having formula (12) below:CH₂═CH—(CH₂)_(p)—O—(AO)_(m)-(EO)_(n)—SO₃M   (12)wherein: AO is a C₃-C₁₈ oxyalkylene group; EO is oxyethylene group; p isa number from 2 to 16; m is a number from 0 to 50; n is a number from 0to 200; and M is a hydrogen atom or a cation.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants prepared from a partially sulfatedphosphate ester reactive surface active agent having formula (13) below:

wherein: e, f, g, and n are each any number; AO is an oxyalkylene groupor an oxy(alkoxymethyl)ethylene group; X denotes a methylene group or acarbonyl group; and M is a hydrogen atom, an alkali metal atom, analkaline earth metal atom, ammonium, a residual group of an alkyl amine,or a residual group of an alkanolamine.

Another type of reactive surfactant that may be suitable for use in thepresent invention are phosphate-type surfactants having formula (14)below:

wherein: R₁ denotes a hydrogen atom or a methyl group; X denotes amethylene group or a carbonyl group; (AO) denotes a polyoxyalkyenegroup; M denotes a hydrogen atom, a metal atom, or ammonium; m denotes anumber equal to 1 or 2; and n denotes a number greater than or equal to1.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (15) below:

wherein: R₁ is a C₆-C₃₀ hydrocarbon group; R₂ is a hydrogen atom or amethyl group; A is a C₂ or C₃ alkylene group; a is equal to 0 or aninteger from 1 to 15; b is an integer from 1 to 15; c is equal to 0 oran integer from 1 to 20; and M is a hydrogen atom, an alkali neutralizedsalt or ammonium of an amine.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (16) below:

wherein: R₁ is a C₆-C₃₀ hydrocarbon; R₂ is a hydrogen atom or a methylgroup; A is an ethylene or propylene group; a is equal to 0 or aninteger from 1 to 15; b is an integer from 1 to 15; c is equal to 0 oran integer from 1 to 20; n is equal to 1 or 2; the sum of m and n isequal to 3; and M is a hydrogen atom, an alkyl metal atom, or analkaline earth metal.

Another type of reactive surfactant that may be suitable for use in thepresent invention are phosphates (or alkali metal salts, alkaline earthmetal salts, alkanolamine salts, or ammonium salts thereof) havingformula (17) below:

wherein: R is a C₆-C₁₂ alkyl group; A is an ethylene group or apropylene group (with the proviso that all the A's cannot be propylenegroups); n is an integer from 1 to 50; q is equal to 1 or 2; r is equalto 1 or 2; s is equal to 0 or 1; the sum of q, r, and s is equal to 3;and X is a methacryloyl group, an acryloyl group, or an allyl group.Reactive surfactants of this type can be obtained by reacting a glycidylcompound (e.g., an acrylic glycidyl ester or allyl glycidyl ether) witha phosphate compound obtained by reacting a polyoxyalkylenealkylcyclohexyl ether with a phosphorylating agent e.g., phosphoricanhydride).

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (18) below:

wherein: R is a hydrogen atom or a methyl group; R₁ is a hydrocarbongroup; M and M′ are each a metal atom or ammonium; and n is an integergreater than or equal to 1.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (19) below:X—O—(R₁O)_(n)-A-SO₃M   (19)wherein: X is a polymerizable group having C═C double bond; M is ahydrogen atom, a metal, or ammonium; R₁ is a hydrocarbon; n is equal to0 or a number greater than or equal to 1; and A is a group having one offormulae (20), (21), or (22) below:

Reactive surfactants of this type may be produced by a method subjectinga compound having polymerizable C═C double bond of formula (23) below:X—O—(R₁O)_(n)—H   (23)to an addition reaction with epichlorohydrin and reacting the resultantchlorohydrin substance with a sulfurous acid salt to yield a sulfonicacid salt. One example of such a reactive surfactant has formula (24)below:

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (25) below:

wherein: R is a hydrogen atom or a methyl group; M is Li, Na, or K; n isa number from 1 to 6; and Rf is a C₁-C₂₀ fluoroalkyl. An example of onesuch surfactant is represented by formula (26) below:

These surfactants may be made by reacting a metallic salt of a succinicacid monoester (e.g., potassium salt of monoallyl succiniate) with afluorine iodide [Rf-(CH₂)_(n)—I] to provide a compound represented byformula (27) below:

This compound is then dissolved in a mixed solvent of water withethanol. A metallic hydrogensulfite (e.g., sodium hydrogensulfite) issubsequently added to yield the reactive surfactant described by formula(25) above. The reactive surfactant is capable of forming a homopolymerof itself or a copolymer thereof with other vinyl monomers.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (28) below:

wherein: R₁ and R₂ are each a hydrocarbon; X is a hydrogen atom or ahydrophilic functional group; Y is a hydrogen atom, a hydrocarbon, orO—(R₃—O)_(c)—R₄ (wherein R₃ is a hydrocarbon, R₄ is a hydrocarbon oracyl group, and c is a number from 1 to 1000); and a and b are each anumber from 0 to 1000. An example of one such surfactant is representedby formula (29) below:

These surfactants may be obtained from a reaction between nonylphenolglycidyl ether and crotonic acid in the presence of a catalyst (e.g.,triethylamine) at 120-130° C.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (30) below:

wherein: A₁ is a C₂-C₄ alkylene; R₁ is a hydrogen atom or a methylgroup; R₂ and R₃ are each a hydrogen atom or a C₁-C₄ hydrocarbon group;R₄ is a C₈-C₂₄ hydrocarbon group or an acyl group; m is a number from 0to 50; and X is a hydrogen atom or a nonionic, anionic, cationic oramphoteric hydrophilic functional group. In certain embodiments, the Xin formula (30) above is a group represented by formula (31) below:-(A²O)_(n)—H   (31)wherein A² is a C₂-C₄ alkylene and n is a number from 1 to 100, or byformula (32) below:-(A30)_(p)—SO₃M¹   (32)wherein: A³ is a C₂-C₄ alkylene; p is a number from 0 to 100; and M¹ isa hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, ora C,-C₄ hydroxyalkylammonium.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (33) below:

wherein: A¹ is a C₂-C₄ alkylene; R¹ is a hydrogen atom or a methylgroup; R₂ and R₃ are each a hydrogen atom or a C₁-C₄ hydrocarbon group;R₄ is a C₈-C₂₄ hydrocarbon group or an acyl group; m is a number from 0to 50; and X is a hydrogen atom or a nonionic, anionic, cationic oramphoteric hydrophilic functional group. In certain embodiments, the Xin formula (33) above is a group represented by formula (34) below:-(A²O)_(n)—H   (34)wherein A² is a C₂-C₄ alkylene and n is a number from 1 to 100, or byformula (35) below:-(A³O)_(p)—SO₃M¹   (35)wherein: A³ is a C₂-C₄ alkylene; p is a number from 0 to 100; and M¹ isa hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, ora C₁-C₄ hydroxyalkylammonium.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (36) and/or (37) below:

wherein: R₁ represents a hydrogen atom or a low class alkyl; R₂represents a C₂-C₄ alkylene; R₃ represents an allyl or methylol group;R₄ represents a hydrogen atom or a low class alkyl; R₅ represents aC₁-C₈ hydrocarbon; m and n each represent a number from 1 to 18; a and ceach represent a number from 0 to 5; b is equal to 0.1; and M₁represents an alkali metal. These surfactants may be made by reactingmaleic methyl oleate with allyl alcohol to prepare maleic methylmonoallyl. N-methyl taurine soda is then added therein to carry outdehydrating condensation to prepare a reactive surfactant represented bythe formula (36) and/or (37) above.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having one or more of formulae (38),(39), (40), or (41) below:

wherein: R₁ is a hydrocarbon group; R₂ is a hydrocarbon group having anallyl or methacrylic group; A is a C₂-C₄ alkylene group; m, n, and p areeach a real number from 0 to 100; R₃ is a hydrogen atom or a low classalkyl group; 1 is equal to 0 or 1; R₄ is a C₁-C₈ alkylene group or aphenylene group; R₅ is a hydrocarbon group having an allyl group or amethacrylic group; and M₁ and M₂ are each a metal or an amine.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (42) below:

wherein: R¹ is a C₆-C₁₈ alkyl group; R₂, R₃, R₄, R₅, and R₆ are each ahydrogen atom, a methyl group; a carboxymethyl group; or a carboxylgroup; X is a hydrogen atom, an ammonium group, an amine base, an alkalimetal, or an alkaline earth metal; Y is a hydrocarbon group having apolymerizable unsaturated group; Z is a nitrile group, a phenyl group,an amide group, or an alkyl carboxylate group; a is an integer from 1 to500; b is an integer from 1 to 100; and c is equal to 0 or is an integerfrom 1 to 250.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (43) below:

wherein: R₁ is a C₈-C₂₂ hydrocarbon (which may have one or moresubstituent groups); R₂ and R₃ are each a C₁-C₃ alkyl group; R₄ is ahydrogen atom or a methyl group; and X is a monovalent anion. An exampleof one such reactive surfactant is3-allyloxy-2-hydroxypropyldimethylstearylammonium chloride.

Another type of reactive surfactant that may be suitable for use in thepresent invention are surfactants having formula (44) and/or (45) below:

wherein: R₁ is a hydrocarbon, phenyl, amino or carboxylic acid residue;R₂ is a hydrogen atom or a methyl group; A is a C₂-C₄ alkylene; n is apositive integer from 1 to 100; M₁ is a monovalent or bivalent cation;and m is the ionic valency of M₁. An example of one such reactivesurfactant is sodium lauryl 2-hydroxy-3-allyloxy-1-propylsulfosuccinate.

Examples of commercially-available reactive surfactants include theHitenol™ and Noigen™ line of reactive surfactants available fromDai-Ichi Kogyo Seiyaku Co., Ltd. of Japan, the Maxemul™ line of reactivesurfactants available from Uniqema of The Netherlands, and the Polystep™RA series of reactive surfactants available from Stepan Co. ofNorthfield, Ill.

Further examples of reactive surfactants that may be suitable for use inthe present invention are described in the following U.S. patents, therelevant disclosures of which are herein incorporated by reference: U.S.Pat. Nos. 6,841,655; 6,649,718; 6,534,597; 6,506,804; 6,242,526;6,239,240; 5,478,883; 5,332,854; 5,324,862; 5,206,286; 4,918,211;4,814,514; 4,611,087; 4,426,489; 4,337,185; 4,246,387; 4,224,455;4,075,411; and 3,541,138. Further examples of suitable reactivesurfactants are described in the following U.S. patent applications, therelevant disclosures of which are herein incorporated by reference: U.S.Patent Application Publication Nos. 2005/0070679; 2004/0242447;2004/0197357; 2004/0048963; and 2003/0181574.

Examples of commercially-available reactive surfactants include theHitenol™ and Noigen™ line of reactive surfactants available fromDai-Ichi Kogyo Seiyaku Co., Ltd. of Japan, the Maxemul™ line of reactivesurfactants available from Uniqema of The Netherlands, and the Polystep™RA series of reactive surfactants available from Stepan Co. ofNorthfield, Ill.

The reactive surfactant may be present in any amount that does notadversely affect the subterranean formation being treated, the proppantparticulate being treated, and/or the properties or components of anyfluid used in conjunction with the present invention (e.g., by forming agel that is too viscous to pump). In certain embodiments, the reactivesurfactant may be present in a treatment fluid used in the presentinvention in an amount in the range of from about 0.01% to about 10% byvolume of the treatment fluid. In certain embodiments, the reactivesurfactant may be present in a treatment fluid used in the presentinvention in an amount in the range of from about 1% to about 5% byvolume of the treatment fluid.

In certain embodiments, the reactive surfactant may perform one or moreadditional functions prior to interacting with the surface beingtreated, including, but not limited to, stabilizing a foam or emulsion,changing the wettability of a surface, solubilizing certain materials,dewatering a fluid, increasing the viscosity of a fluid, reducing thesurface tension of a fluid, enhancing viscoelastic or rheologicalproperties of a fluid, stabilizing a film or coating on a surface,and/or aiding in the placement of a treatment fluid in a subterraneanformation. In certain embodiments, after interacting with the surfacebeing treated, the reactive surfactant may be capable of interactingwith some other substance introduced to the surface of the particulate(e.g., a resin or tackifying agent subsequently introduced into thesubterranean formation). In those embodiments, the reactive surfactantmay, inter alia, “disappear” from the surface being treated or becomeadsorbed into the surface and/or into a coating on that surface, whichmay impart the functionality of the surfactant (e.g., reactivity,curability, spreadability, wettability, hydrophobicity, orhydrophilicity) to the surface and/or any coating residing thereon.

In certain embodiments of the present invention, a resin and/ortackifying agent optionally may be allowed to interact with the surfacebeing treated, among other purposes, to help consolidate and/orstabilize unconsolidated particulates, modify the hydrophobicity orhydrophilicity of the surface of the particulate, and/or maintain theconductivity of a subterranean formation, gravel pack, and/or proppantpack. The optional resin or tackifying agent may be provided as acomponent of a treatment fluid to be introduced into a subterraneanformation, or it may be pre-applied to a proppant particulate (e.g., asurfactant-treated proppant particulate of the present invention). Theoptional resin or tackifying agent may comprise any such substance knownand suitable for use in subterranean operations. Suitable resins mayinclude, but are not limited to, two component epoxy based resins,novolak resins, polyepoxide resins, phenol-aldehyde resins,urea-aldehyde resins, urethane resins, phenolic resins, furan resins,furan/furfuryl alcohol resins, phenolic/latex resins, phenolformaldehyde resins, polyester resins and hybrids and copolymersthereof, polyurethane resins (and hybrids and copolymers thereof),acrylate resins, and mixtures thereof. Suitable tackifying agents mayinclude, but are not limited to, include non-aqueous tackifying agents,aqueous tackifying agents, silyl-modified polyamides, aqueous andnon-aqueous gelable polymer compositions, and mixtures thereof. Theapplication of the optional resin or tackifying agent may furtherrequire the application of one or more preflush fluids, afterflushfluids, catalysts, or other additives, among other purposes, to preparea surface of a particulate for placement of the resin or tackifyingagent and/or to activate the resin or tackifying agent. The optionalresin or tackifying agent may be provided prior to, during, orsubsequent to any portion of a method of the present invention, and maybe provided as a component of a treatment fluid comprising the reactivesurfactant and/or in a separate treatment fluid. A person skilled in theart, with the benefit of this disclosure, will recognize when the use ofan optional resin or tackifying agent is appropriate for a particularapplication of the present invention, as well as the type of resin ortackifying agent to use and the appropriate method of applying thatresin or tackifying agent to a particulate and/or subterraneanformation. In those embodiments where an optional resin or tackifyingagent is used, the reactive surfactant may, inter alia, aid in theplacement of the resin or tackifying agent, activate the resin ortackifying agent, and/or become adsorbed into a coating formed on thesurface being treated by the resin or tackifying agent.

Proppant particulates suitable for the present invention, including thesurfactant-treated proppant particulates of the present invention, maycomprise any particulate suitable for use in subterranean operations. Itshould be understood that the term “proppant particulate,” as usedherein, includes all known shapes of materials including substantiallyspherical materials, fibrous materials, polygonal materials (e.g., cubicmaterials), and mixtures thereof. Suitable proppant particulatesinclude, but are not limited to, sand, bauxite, ceramic materials, glassmaterials (e.g., glass beads), polymer materials, Teflon® materials, nutshell pieces, seed shell pieces, cured resinous particulates comprisingnut shell pieces, cured resinous particulates comprising seed shellpieces, fruit pit pieces, cured resinous particulates comprising fruitpit pieces, wood, composite particulates and combinations thereof.Suitable composite particulates may comprise a binder and a fillermaterial wherein suitable filler materials include silica, alumina,fumed carbon, carbon black, graphite, mica, titanium dioxide,meta-silicate, calcium silicate, kaolin, talc, zirconia, boron, fly ash,hollow glass microspheres, solid glass, ground nut/seed shells or husks,saw dust, ground cellulose fiber, and combinations thereof. The proppantparticulates may have a size in the range of from about 2 to about 400mesh, U.S. Sieve Series. In particular embodiments, preferredparticulates size distribution ranges are one or more of 6/12 mesh,8/16, 12/20, 16/30, 20/40, 30/50, 40/60, 40/70, or 50/70 mesh.

The treatment fluids of the present invention generally comprise a basefluid and a reactive surfactant and/or a surfactant-treated proppantparticulate of the present invention. The base fluid may comprise anyfluid suitable for use in subterranean operations that does not containcompounds that adversely affect other components of the treatment fluid.The base fluid used in the treatment fluids of the present invention maybe aqueous-based, non-aqueous-based, or a combination thereof. Where thebase fluid is aqueous-based, it may comprise fresh water, salt water(e.g., water containing one or more salts dissolved therein), a brine,seawater, or a combination thereof. Where the base fluid isnon-aqueous-based, the base fluid may comprise any number of organicliquids. Examples of suitable organic liquids include, but are notlimited to, mineral oils, synthetic oils, esters, and the like.

The treatment fluids of the present invention optionally may compriseany number of additional additives, including, but not limited to,salts, additional surfactants, acids, fluid loss control additives, gas,foamers, emulsifiers, demulsifiers, defoamers, antifoamers, corrosioninhibitors, scale inhibitors, catalysts, clay control agents, biocides,friction reducers, bridging agents, dispersants, flocculants, H₂Sscavengers, CO₂ scavengers, oxygen scavengers, lubricants, viscosifiers,breakers, pH adjusting agents, weighting agents, relative permeabilitymodifiers, resins, tackifying agents, particulate materials (e.g.,proppant particulates), wetting agents, coating enhancement agents, andthe like. A person skilled in the art, with the benefit of thisdisclosure, will recognize the types of additives that may be includedin the treatment fluid for a particular application depending upon,among other factors, the type of reactive surfactant used, thecomposition of the treatment fluid, the composition of the subterraneanformation and/or particulates being treated, and the like.

The methods of the present invention generally comprise the use of areactive surfactant to treat surfaces within a subterranean formation(e.g., formation fines, proppant particulates, fractures faces, proppedfracture faces or well bore walls) or proppant particulates for use in atreatment fluid, and/or the use of a proppant particulate that has beentreated with a reactive surfactant.

In certain embodiments, the methods of the present invention comprise:providing a treatment fluid of the present invention that comprises abase fluid and a reactive surfactant; introducing the treatment fluidinto a subterranean formation; and allowing the reactive surfactant tointeract with a surface residing within the subterranean formation. Inthese embodiments, the surface residing within the subterraneanformation may comprise, among other things, a fracture face, a proppedfracture face, a well bore wall, a surface of sand particulates, gravelparticulates, fines, proppant particulates placed in the subterraneanformation (e.g., during the course of a hydraulic fracturing treatment),or any other type of particulates found within the subterraneanformation. In these embodiments, the treatment fluid comprising thereactive surfactant may comprise a low-viscosity (e.g., lightly gelledor not gelled) aqueous solution, which may be injected into thesubterranean formation by any means known in the art (e.g., through thetubing, casing, wellbore, coiled tubing, annulus, jetting, acousticalpulsing, etc.).

In certain embodiments, the methods of the present invention comprise:providing a treatment fluid of the present invention that comprises abase fluid and a proppant particulate of the present invention thatcomprises at least one surface that has been allowed to interact with areactive surfactant; and introducing the treatment fluid into asubterranean formation. In certain embodiments, at least some portion ofthe reactive surfactant may reside on a surface of a proppantparticulate of the present invention. The proppant particulate of thepresent invention may be deposited in the subterranean formation, amongother purposes, to form a portion of a gravel pack and/or to hold openconductive channels or fractures within the subterranean formation(e.g., forming a “proppant pack” within a subterranean fracture). Incertain embodiments, the treatment fluid may be introduced into thesubterranean formation at or above a pressure sufficient to create orenhance one or more fractures within the subterranean formation whereinthe proppant particulates of the present invention may be deposited.“Enhancing” one or more fractures in a subterranean formation mayinclude the extension or enlargement of one or more natural orpreviously created fractures in the subterranean formation.

In certain embodiments, the methods of the present invention comprise:providing a proppant particulate; providing a reactive surfactant; andallowing the reactive surfactant to interact with a surface of theproppant particulate. The reactive surfactant may be allowed to interactwith the surface of the proppant particulate in any suitable mannerknown in the art. For example, the reactive surfactant and proppantparticulate may be mixed together in a treatment fluid and allowed tointeract therein. These components may be mixed together in a treatmentfluid prior to, during (e.g., “on the fly”), or subsequent tointroducing one or more of those components into a subterraneanformation and/or a well bore penetrating that subterranean formation. Incertain embodiments, allowing the reactive surfactant to interact withthe surface of the proppant particulate may result in some portion ofthe reactive surfactant becoming attached to the surface of the proppantparticulate and/or becoming adsorbed into the surface of the particulate(or a coating thereon). A proppant particulate treated using thesemethods of the present invention then may be used in a variety ofsubterranean operations, including, but not limited to, hydraulicfracturing operations.

The reactive surfactants used in the methods of the present inventionmay be used in or in conjunction with numerous subterranean treatments,including but not limited to proppant fracturing, gravel packing,“frac-packing,” screened completions, screenless completions, drillingfluids, acidizing (e.g., matrix acidizing or fracture acidizing),conformance treatments (e.g., water control, relative permeabilitymodifiers, etc), other sand control applications (e.g., formationconsolidation, near wellbore consolidation, etc.), fluid loss “pills”,scale treatments, hydrate control treatments, and the like.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Whilenumerous changes may be made by those skilled in the art, such changesare encompassed within the spirit of this invention as defined by theappended claims. The particular embodiments disclosed above areillustrative only, as the present invention may be modified andpracticed in different but equivalent manners apparent to those skilledin the art having the benefit of the teachings herein. Furthermore, nolimitations are intended to the details of construction or design hereinshown, other than as described in the claims below. It is thereforeevident that the particular illustrative embodiments disclosed above maybe altered or modified and all such variations are considered within thescope and spirit of the present invention. In particular, every range ofvalues (e.g., “from about a to about b,” or, equivalently, “fromapproximately a to b,” or, equivalently, “from approximately a-b”)disclosed herein is to be understood as referring to the power set (theset of all subsets) of the respective range of values. The terms in theappended claims have their plain, ordinary meaning unless otherwiseexplicitly and clearly defined by the patentee.

1. A proppant particulate comprising at least one treated surface thathas interacted with a reactive surfactant.
 2. The proppant particulateof claim 1 wherein at least a portion of the reactive surfactant resideson the treated surface of the proppant particulate.
 3. The proppantparticulate of claim 1 wherein the proppant particulate is selected fromthe group consisting of sand, bauxite, ceramic materials, glassmaterials, polymer materials, nut shell pieces, seed shell pieces, curedresinous particulates comprising nut shell pieces, cured resinousparticulates comprising seed shell pieces, fruit pit pieces, curedresinous particulates comprising fruit pit pieces, wood, compositeparticulates, and combinations thereof.
 4. The proppant particulate ofclaim 1 wherein the reactive surfactant is selected from the groupconsisting of diallyl amine pluronics, linoieic alcohols, allyl alkylphenols, acrylate derivatives, allyl alcohol alkenyl anhydridederivatives, maleic derivatives, sulfosuccinate derivatives, allyl aminesalts, derivatives thereof, and combinations thereof.
 5. The proppantparticulate of claim 1 further comprising a resin and/or tackifyingagent.
 6. The proppant particulate of claim 5 wherein the resin isselected from the group consisting of two component epoxy based resins,novolak resins, polyepoxide resins, phenol- aldehyde resins,urea-aldehyde resins, urethane resins, phenolic resins, furan resins,furan/furfuryl alcohol resins, phenolic/latex resins, phenolformaldehyde resins, polyester resins, polyurethane resins, acrylateresins, derivatives thereof and combinations thereof.
 7. The proppantparticulate of claim 5 wherein the tackifying agent is selected from thegroup consisting of non-aqueous tackifying agents, aqueous tackifyingagents, silyl-modified polyamides, aqueous gelable polymer compositions,non-aqueous gelable polymer compositions, derivatives thereof andcombinations thereof.
 8. A treatment fluid comprising a base fluid and areactive surfactant.
 9. The treatment fluid of claim 8 wherein thereactive surfactant is selected from the group consisting of diallylamine pluronics, linoieic alcohols, allyl alkyl phenols, acrylatederivatives, allyl alcohol alkenyl anhydride derivatives, maleicderivatives, sulfosuccinate derivatives, allyl amine salts, derivativesthereof and combinations thereof,
 10. The treatment fluid of claim 8wherein the reactive surfactant is present in an amount in the range offrom about 1% to about 5% by volume of the treatment fluid.
 11. Thetreatment fluid of claim 8 further comprising a resin and/or tackifyingagent.
 12. The treatment fluid of claim 8 further comprising a pluralityof proppant particulates.
 13. The treatment fluid of claim 12 whereinthe proppant particulate is selected from the group consisting of sand,bauxite, ceramic materials, glass materials, polymer materials, nutshell pieces, seed shell pieces, cured resinous particulates comprisingnut shell pieces, cured resinous particulates comprising seed shellpieces, fruit pit pieces, cured resinous particulates comprising fruitpit pieces, wood, composite particulates, and combinations thereof. 14.The treatment fluid of claim 12 wherein the plurality of proppantparticulates comprises one or more proppant particulates that compriseat least one treated surface that has interacted with a reactivesurfactant.
 15. The treatment fluid of claim 8 further comprising anadditive selected from the group consisting of salts, surfactants,acids, fluid loss control additives, gas, foamers, emulsifiers,demulsifiers, defoamers, antifoamers, corrosion inhibitors, scaleinhibitors, catalysts, clay control agents, biocides, friction reducers,bridging agents, dispersants, flocculants, H₂S scavengers, CO₂scavengers, oxygen scavengers, lubricants, viscosifiers, breakers, pHadjusting agents, weighting agents, relative permeability modifiers,wetting agents, coating enhancement agents, and combinations thereof.16. A treatment fluid comprising a base fluid and a proppant particulatethat comprises at least one treated surface that has interacted with areactive surfactant.
 17. The treatment fluid of claim 16 furthercomprising a reactive surfactant.
 18. The treatment fluid of claim 16wherein the reactive surfactant is selected from the group consisting ofdiallyl amine pluronics, linoieic alcohols, allyl alkyl phenols,acrylate derivatives, allyl alcohol alkenyl anhydride derivatives,maleic derivatives, sulfosuccinate derivatives, allyl amine salts,derivatives thereof and combinations thereof.
 19. The treatment fluid ofclaim 16 wherein the proppant particulate is selected from the groupconsisting of sand, bauxite, ceramic materials, glass materials, polymermaterials, nut shell pieces, seed shell pieces, cured resinousparticulates comprising nut shell pieces, cured resinous particulatescomprising seed shell pieces, fruit pit pieces, cured resinousparticulates comprising fruit pit pieces, wood, composite particulates,and combinations thereof.
 20. The treatment fluid of claim 16 furthercomprising a resin and/or tackifying agent.